CN107051424B - A catalyst for low-temperature catalytic combustion of chlorinated hydrocarbon compounds, preparation method and application thereof - Google Patents
A catalyst for low-temperature catalytic combustion of chlorinated hydrocarbon compounds, preparation method and application thereof Download PDFInfo
- Publication number
- CN107051424B CN107051424B CN201710174182.8A CN201710174182A CN107051424B CN 107051424 B CN107051424 B CN 107051424B CN 201710174182 A CN201710174182 A CN 201710174182A CN 107051424 B CN107051424 B CN 107051424B
- Authority
- CN
- China
- Prior art keywords
- tungsten
- catalyst
- catalytic combustion
- chlorinated hydrocarbon
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 37
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 52
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000010937 tungsten Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 18
- 238000011068 loading method Methods 0.000 claims abstract description 15
- -1 pharmaceutical Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000002485 combustion reaction Methods 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000004809 Teflon Substances 0.000 claims 1
- 229920006362 Teflon® Polymers 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000460 chlorine Substances 0.000 abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 abstract description 11
- 231100000572 poisoning Toxicity 0.000 abstract description 6
- 230000000607 poisoning effect Effects 0.000 abstract description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 abstract description 3
- 239000010985 leather Substances 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000004753 textile Substances 0.000 abstract description 2
- 239000002023 wood Substances 0.000 abstract description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 38
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 20
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 18
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229940117389 dichlorobenzene Drugs 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000001193 catalytic steam reforming Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 238000000520 microinjection Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002539 nanocarrier Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 125000005430 oxychloro group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种用于氯代烃类化合物低温催化燃烧的催化剂，其由载体纳米氧化铈和负载的钨组成，其中钨是以氧化钨的形式存在，按重量计算，钨元素的负载量为1～20％。本发明还公开了所述催化剂的制备方法以及所述催化剂在氯代烃类化合物低温催化燃烧中的应用。所述的催化剂相较于未负载钨的纳米氧化铈，催化活性有了显著的提高，对于氯代脂肪烃、氯代芳香烃具有优异的催化活性，而且具有抗氯中毒能力强、寿命长等特点，可以广泛用于纺织、制药、制革、木材加工中产生的氯代烃类化合物的低温催化净化。本发明的催化剂的制备方法工艺简单、原料价格低廉。The invention discloses a catalyst for low-temperature catalytic combustion of chlorinated hydrocarbon compounds, which is composed of a carrier nano-cerium oxide and supported tungsten, wherein the tungsten exists in the form of tungsten oxide. Calculated by weight, the supported amount of tungsten element 1 to 20%. The invention also discloses the preparation method of the catalyst and the application of the catalyst in the low-temperature catalytic combustion of the chlorinated hydrocarbon compound. Compared with the nano-cerium oxide without tungsten loading, the catalyst has significantly improved catalytic activity, has excellent catalytic activity for chlorinated aliphatic hydrocarbons and chlorinated aromatic hydrocarbons, and has strong resistance to chlorine poisoning, long life, etc. It can be widely used in low-temperature catalytic purification of chlorinated hydrocarbon compounds produced in textile, pharmaceutical, leather and wood processing. The preparation method of the catalyst of the invention has simple process and low price of raw materials.
Description
Technical Field
The invention belongs to the technical field of catalytic combustion of organic compounds, and particularly relates to a catalyst for low-temperature catalytic combustion of chlorinated hydrocarbon compounds, a preparation method of the catalyst and application of the catalyst in low-temperature catalytic combustion of chlorinated hydrocarbon compounds.
Background
chlorine-Containing Volatile Organic Compounds (CVOCs) can not only cause serious harm to human health, but also 12 first-ranked persistent organic pollutants in the International treaty on environmental projects of United nations are chlorine-containing organic compounds. Strict environmental regulations are set by many countries for emissions of CVOCs. The chlorine-containing volatile hydrocarbons are classified into nonaromatic aliphatic hydrocarbon chlorides such as dichloroethane, trichloroethylene, methyl chloride and polychlorinated methane, and aromatic hydrocarbon chlorides such as chlorobenzene and dichlorobenzene. The former is produced in the processes of producing vinyl chloride by the oxychlorination method in the chlor-alkali industry, tanning, washing, pharmaceutical industry, etc., and the latter is produced in the bleaching of wood pulp with a chlorine-based oxidizing agent, the heat treatment of chlorine-containing compounds, the recovery of metals, etc. Since these emissions are industrial processes related to the nationwide population and the emission of a large amount of CVOCs is unavoidable, there is no possibility of eliminating pollution from the source. And the method adopting post-treatment to eliminate the pollution caused by CVOCs becomes the only feasible way and method.
At present, a plurality of methods for comprehensive control of CVOCs exist, and at present, methods for removing chlorine-containing organic matters mainly include direct combustion, adsorption methods, absorption methods, photocatalysis, catalytic hydrodechlorination, catalytic steam reforming, catalytic combustion and the like. The catalytic combustion has low operation temperature (250-550 ℃), wide pollutant eliminating concentration and products (CO)2HCl and H2O) high selectivity and the like. Therefore, the catalytic combustion has the effect of eliminating volatilityThe organic compound is widely applied.
Chlorinated aromatic hydrocarbons such as chlorobenzene, polychlorobenzene and dioxin are mainly produced in the incineration process of garbage. Due to the high toxicity of such species, chlorobenzene, dichlorobenzene, chlorophenol and the like are generally used as model molecules for screening and investigating the catalyst under experimental conditions.
The use of CVOCs catalytic combustion has mainly focused on three types of catalysts: noble metal catalysts, solid acid catalysts, transition metal oxide catalysts. The noble metal catalyst has the problems of relatively high price, high chlorination activity (easily generating polychlorinated byproducts with higher toxicity), easy poisoning by generating oxychloro compounds, poisoning in a high-temperature area due to loss of noble metals and the like, so that the application of the noble metal catalyst is limited. The transition metal catalyst for catalytic combustion of chloro-aromatic hydrocarbon is mainly V2O5-TiO2-based catalysts and the like. However, V2O5-TiO2V in the base catalyst2O5Has toxicity and is easy to cause secondary pollution, thus limiting the application of the pesticide. Other types of catalysts, such as solid acid catalysts, have some applications and have not been widely popularized due to their low activity or high number of by-products.
The transition metal oxide, which is the main catalyst active component used in the patent literature, is UO2、MnO2、Co3O4、La2O3、CeO2Etc. and noble metals Pt, Pd, etc., and SiO as carrier2、Al2O3、TiO2、ZrO2. Representative patents are JP 2002219364, JP 2001286729, JP2001278630, JP 2001009284, JP 2001286734, JP 2001327869, JP 10085559a2, U.S. patent 4031149, U.S. patent 4059677, U.S. patent4065543, U.S. patent 4561969, U.S. patent 58116628, U.S. patent 4169862, U.S. patent7052663, and the like.
Disclosure of Invention
The invention aims to provide a catalyst for low-temperature catalytic combustion of chlorinated hydrocarbon compounds, which has high catalytic activity, strong chlorine poisoning resistance and long service life.
The catalyst comprises carrier nano cerium oxide and loaded tungsten, wherein the tungsten exists in the form of tungsten oxide, and the loading amount of tungsten element is 1-20%, preferably 1-8%, and more preferably 4-8% by weight.
Another object of the present invention is to provide a method for preparing the catalyst, which comprises the steps of:
A. preparing a nano cerium oxide carrier by a hydrothermal method;
B. and B, according to the loading amount of tungsten, soaking the water solution of the tungsten precursor with the corresponding volume into the nano cerium oxide carrier prepared in the step A, uniformly stirring, standing, drying, and roasting at 400-500 ℃ for 1.5-3 hours to obtain the catalyst.
In a preferred embodiment of the present invention, the hydrothermal method in step a specifically comprises: mixing and dissolving cerium nitrate and urea in water, uniformly stirring, then putting into a crystallization kettle with a polytetrafluoroethylene lining, crystallizing at 120-160 ℃ for 4-6 h, cooling to room temperature, filtering, washing and drying precipitates, and roasting at 400-500 ℃ for 1.5-4 h to obtain the nano cerium oxide carrier.
Preferably, the roasting process of the steps A and B is as follows: heating was started at 50 ℃ and programmed to 450 ℃ at a rate of 100 ℃/h and baked at 450 ℃ for 2 hours.
Preferably, the tungsten precursor is ammonium tungstate, and the concentration of tungsten element in the aqueous solution of the tungsten precursor is 50-70 g/L.
The invention also aims to disclose the application of the catalyst in the low-temperature catalytic combustion of the chlorinated hydrocarbon compound.
The application is specifically a method for low-temperature catalytic combustion of chlorinated hydrocarbon compounds, and the combustion conditions of the method are as follows: the catalyst is the catalyst, the reaction pressure is 0.1-0.5 MPa, the concentration of the chlorinated hydrocarbon compound is 100-5000 ppm, the oxygen concentration is 0-20 vol%, the reaction temperature is 100-500 ℃, and the space velocity is 1000-100000/hour.
The invention has the beneficial effects that:
the method adopts a hydrothermal method to prepare the nano cerium oxide carrier, and realizes the loading of tungsten by an immersion method, and the preparation method has simple process and low raw material price. Compared with the nano cerium oxide without tungsten, the obtained nano cerium oxide carrier-supported tungsten catalyst has the advantages of remarkably improved catalytic activity, excellent catalytic activity on chlorinated aliphatic hydrocarbon and chlorinated aromatic hydrocarbon, strong chlorine poisoning resistance, long service life and the like, and can be widely used for low-temperature catalytic purification of chlorinated hydrocarbon compounds generated in textile, pharmacy, leather making and wood processing.
Detailed Description
The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
Comparative example 1 preparation of nano cerium oxide support
Mixing 10g of commercially available cerium nitrate and 3g of commercially available urea, adding 40mL of deionized water for dissolving, violently stirring for half an hour by using a magneton stirrer, then putting into a crystallization kettle with a polytetrafluoroethylene lining, standing at 140 ℃ for crystallization for 5 hours, cooling to room temperature, filtering and washing by using deionized water until the solution is neutral, drying in a drying oven at 110 ℃ for 12 hours, and then roasting in a muffle furnace at 450 ℃, wherein the specific roasting process is as follows: heating at 50 deg.C, programming at a rate of 100 deg.C/hr for 4 hr, and calcining at 450 deg.C for 2 hr to obtain nanometer cerium oxide carrier (powder) designated as CeO2。
Examples 1-5 preparation of Nano cerium oxide Supported tungsten catalyst
Commercially available ammonium tungstate was prepared as an aqueous solution having a concentration of tungsten element of 60g/L, and examples 1 to 5 were each prepared by impregnating 1g of a nano-cerium oxide support (prepared by the method of comparative example 1) with a corresponding volume of the aqueous solution of ammonium tungstate, as shown in Table 1. Stirring uniformly, standing overnight in air at room temperature, drying in a 110 ℃ oven for 12 hours, and roasting, wherein the specific roasting process is as follows: heating at 50 deg.C, programming at a rate of 100 deg.C/hr for 4 hr, and calcining at 450 deg.C for 2 hr to obtain powder as the nanometer cerium oxide supported tungsten catalyst.
The tungsten oxide loading of example 1 was 1% by weight and is labeled as 1 wt% W/CeO2(ii) a Example 2 has a tungsten loading of 2%, labeled 2 wt% W/CeO2(ii) a Example 3 has a tungsten loading of 4%, labeled 4 wt% W/CeO2(ii) a Example 4 has a tungsten loading of 8%, labeled 8 wt% W/CeO2(ii) a Example 5 has a tungsten loading of 20%, labeled 20 wt% W/CeO2。
TABLE 1 tungsten loading and chlorobenzene catalytic combustion results of examples 1-5
Example 6: catalytic combustion of catalysts of different tungsten loadings
The catalysts of examples 1 to 5 and comparative example 1 were used to perform low-temperature catalytic combustion tests of chlorobenzene, all of which were carried out in a fixed-bed microreactor (quartz with an inner diameter of 3 mm), with the amount of catalyst being 200mg and the temperature being automatically controlled by a K-type thermocouple. Chlorobenzene was injected into a vaporization chamber using a 100 series KDS120 microinjection pump from Stoelting corporation, usa, and then mixed with air into a reactor for combustion. The total flow rate was controlled by a mass flow meter, the concentration of chlorobenzene was 1000ppm, the amount of exhaust gas treated per gram of catalyst per hour was 30L, the linear velocity of the gas passing through the reactor was 100 m/hour, and the reaction pressure was normal pressure. The relationship between the chlorobenzene conversion and the reaction temperature is shown in Table 1, wherein T10％、T50％、T90％The reaction temperatures required for the conversions to 10%, 50% and 90%, respectively. The main reaction products are carbon dioxide, hydrogen chloride and a small amount of chlorine.
Compared with comparative example 1 without tungsten, the catalytic activity of the catalyst of examples 1-4 is remarkably improved, and the activity sequence of the nano carrier and the catalyst loaded with tungsten is as follows: 8 wt% W/CeO2>4wt％W/CeO2>2wt％W/CeO2>1wt％W/CeO2>CeO2。
EXAMPLE 7 catalytic Combustion of Chlorobenzenes at various concentrations
A burning test was conducted on the catalyst of example 3 by changing the chlorobenzene concentration to 500ppm and 2000ppm according to the procedure of example 6, respectively, and the burning results are shown in Table 2, except that the reaction conditions were not changed.
TABLE 2 catalytic Combustion results on catalyst of example 3 with different concentrations of chlorobenzene
As shown in Table 2, when the concentration of chlorobenzene is 500-2000 ppm, the catalysts in example 3 have high catalytic activity, and can be widely used for catalytic combustion elimination of chlorinated aromatic hydrocarbons with different concentrations. The catalytic activity increases in the catalytic combustion of chlorobenzene at lower concentrations, while it decreases slightly as the chlorobenzene concentration increases.
EXAMPLE 8 catalytic Combustion of chlorobenzene at different exhaust gas treatment levels
The combustion test was conducted on the catalysts of comparative example 1, example 3 and example 4 in accordance with the procedure of example 6, respectively, and the amount of exhaust gas treated per gram of catalyst per hour was changed to 15 and 60L, while the remaining reaction conditions were unchanged, and the combustion results are shown in Table 3.
TABLE 3 catalytic combustion results of chlorobenzene with different waste gas treatment amounts
The activity difference of the catalysts of the comparative example 1, the example 3 and the example 4 is obvious under different exhaust gas treatment amounts, and the catalytic activity of the catalysts of the examples 3 and 4 is still obviously higher than that of the comparative example 1 under the condition of high treatment amount, which shows that the synergistic effect of tungsten and cerium can effectively reduce the catalytic combustion temperature of chlorobenzene. The chlorobenzene catalysts with different waste gas treatment amounts have the following activity sequences: 8 wt% W/CeO2>4wt％W/CeO2>CeO2。
From the results of examples 6 to 8, it is clear that the tungsten loading has a great influence on the catalytic activity of the catalyst of the present inventionUnder the conditions of same reaction concentration and different waste gas treatment amounts, the catalytic combustion activity of the tungsten catalyst loaded by the nano cerium oxide is 8 wt% of W/CeO2>4wt％W/CeO2>2wt％W/CeO2>1wt％W/CeO2>CeO2I.e., at least in the range of 1-8%, the catalytic activity of the catalyst is enhanced as the tungsten loading increases.
EXAMPLE 9 catalytic Combustion of various chlorinated hydrocarbons
The procedure of example 6 was followed to carry out a combustion test of methylene chloride, dichloroethane, trichloroethylene and dichlorobenzene respectively on the catalyst of example 3, and the combustion results are shown in Table 4, except that the reaction conditions were not changed.
Table 4 catalytic combustion results of different chlorinated hydrocarbons on the catalyst of example 3
The catalyst of example 3 shows excellent catalytic combustion activity of dichloromethane, dichloroethane and trichloroethylene, and the activity of dichlorobenzene is consistent with that of chlorobenzene. The catalyst in the embodiment 3 has excellent catalytic activity on chlorinated aliphatic hydrocarbon and chlorinated aromatic hydrocarbon, can be widely applied to catalytic combustion of chlorinated hydrocarbon, and has industrial application advantages and significance for treatment of various chlorinated hydrocarbon waste gases.
Example 10 catalytic Combustion stability testing of the catalyst
The burning test was performed on the catalysts of comparative example 1 and example 3, respectively, according to the method of example 6, with the reaction temperature controlled at 250 c or 350 c, and the remaining reaction conditions were not changed, and the results of the catalytic burning stability test of the catalysts are shown in table 5.
TABLE 5 catalytic combustion stability of catalysts at different temperatures
Example 3 exhibited superior resistance to chlorine poisoning and catalytic combustion stability at different temperatures compared to comparative example 1. The chlorobenzene conversion in example 3 was maintained above 90% in 50 hours by catalytic combustion at 350 ℃. The product analysis shows that the main products are carbon dioxide, hydrogen chloride and chlorine, which can not cause secondary pollution and has good industrial application prospect.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710174182.8A CN107051424B (en) | 2017-03-22 | 2017-03-22 | A catalyst for low-temperature catalytic combustion of chlorinated hydrocarbon compounds, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710174182.8A CN107051424B (en) | 2017-03-22 | 2017-03-22 | A catalyst for low-temperature catalytic combustion of chlorinated hydrocarbon compounds, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107051424A CN107051424A (en) | 2017-08-18 |
| CN107051424B true CN107051424B (en) | 2022-03-22 |
Family
ID=59620110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710174182.8A Active CN107051424B (en) | 2017-03-22 | 2017-03-22 | A catalyst for low-temperature catalytic combustion of chlorinated hydrocarbon compounds, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107051424B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126798A (en) * | 2018-07-18 | 2019-01-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Supported cobalt-base catalyst and its preparation method and application for vinyl chloride low-temperature catalytic oxidation |
| CN111774052A (en) * | 2020-06-19 | 2020-10-16 | 华中科技大学 | Cerium oxide nanorods decorated with high melting point rare metal elements and their preparation and application |
| CN112371106A (en) * | 2020-11-30 | 2021-02-19 | 绍兴文理学院 | Synthesis method and application of Ce-Nb-O composite metal oxide catalyst |
| CN115400745A (en) * | 2022-07-28 | 2022-11-29 | 常州大学 | Cerium-based catalyst for efficiently degrading CVOCs (chemical vapor deposition) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1157255C (en) * | 2000-03-22 | 2004-07-14 | 中国科学院大连化学物理研究所 | Metal oxide catalyst for clearing halogenated aromatic through catalytic oxidation |
| CN100341787C (en) * | 2005-03-29 | 2007-10-10 | 中国科学院大连化学物理研究所 | Cerium oxide nano materials and its preparation and use |
-
2017
- 2017-03-22 CN CN201710174182.8A patent/CN107051424B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107051424A (en) | 2017-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107051424B (en) | A catalyst for low-temperature catalytic combustion of chlorinated hydrocarbon compounds, preparation method and application thereof | |
| CN107008459B (en) | Catalyst for low-temperature catalytic combustion of chlorine-containing organic matter and its preparation method and application | |
| CN103894200A (en) | Method and catalyst for low-temperature catalytic combustion elimination of polychlorinated aromatic hydrocarbon | |
| CN109603869B (en) | Phosphoric acid modified cerium oxide catalyst and preparation method and application thereof | |
| CN103357415A (en) | Catalyst for catalytic combustion of chlorine-containing organic waste gas | |
| CN101185796A (en) | A kind of chlorinated aromatic hydrocarbon exhaust gas catalytic purification method | |
| CN109364938A (en) | A kind of cobalt manganese catalyst for oxidative elimination of volatile organic compounds and preparation method thereof | |
| CN110586073A (en) | Catalyst for removing dioxin in kiln flue gas through catalytic oxidation and preparation method thereof | |
| CN111330606A (en) | Catalyst for high-efficiency degradation of chlorine-containing organic waste gas at low temperature, preparation method and application thereof | |
| CN113786828A (en) | Catalyst for synergistic removal of NOx and CVOCs and preparation method and application thereof | |
| CN105289716A (en) | Catalyst for volatile halocarbon catalytic combustion and its preparation method and use | |
| CN112604700A (en) | Phosphorylated perovskite catalyst and preparation method and application thereof | |
| CN106890635A (en) | A kind of catalyst for chloride VOC low-temperature catalytic burning and its preparation method and application | |
| CN110935470B (en) | Preparation method of exhaust gas purification catalyst | |
| CN103962134A (en) | Method for eliminating chloro aromatic hydrocarbon through low-temperature catalytic combustion | |
| CN109833864A (en) | One kind catalyst for catalytic combustion of VOCs containing halogen and preparation method thereof | |
| CN105251476B (en) | A kind of CeO2‑Cr2O3‑Nb2O5The preparation method of composite oxide catalysts | |
| CN109261144B (en) | Catalyst for chlorine-containing organic waste gas treatment process | |
| KR20040094522A (en) | Catalyst for Removing Aromatic Halogenated Compounds Comprising Dioxin, Carbon Monoxide, and Nitrogen Oxide and Use Thereof | |
| KR101839778B1 (en) | A method for producing an metal aluminate oxidation catalyst having improved endotoxicity against organic chloro compounds and an oxidation catalyst | |
| JPH0857323A (en) | Catalyst for decomposition of volatile organic halogen compound and production thereof | |
| JP5041848B2 (en) | Method for treating halogenated aliphatic hydrocarbon-containing gas | |
| KR100390770B1 (en) | Multifunctional oxidation catalysts for removal of chlorinated volatile organic compounds | |
| CN112682806B (en) | Method for eliminating chlorine-containing volatile organic pollutants through high-temperature catalytic combustion | |
| JP3760090B2 (en) | Organohalogen compound decomposition catalyst and method for treating organohalogen compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |